CN113402507B - Triphenylene derivative, light-emitting device material, and light-emitting device - Google Patents

Triphenylene derivative, light-emitting device material, and light-emitting device Download PDF

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CN113402507B
CN113402507B CN202110782424.8A CN202110782424A CN113402507B CN 113402507 B CN113402507 B CN 113402507B CN 202110782424 A CN202110782424 A CN 202110782424A CN 113402507 B CN113402507 B CN 113402507B
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CN113402507A (en
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王鹏
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Zhejiang Huadisplay Optoelectronics Co Ltd
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Abstract

The present invention relates to a triphenylene derivative for an organic light-emitting element, a light-emitting device material containing the triphenylene derivative, and a light-emitting device, and more particularly, to a soluble organic compound having excellent color purity and high luminance and light-emitting efficiencyAnd an OLED device using the same. Characterized by the following general formula (1)

Description

Triphenylene derivative, light-emitting device material, and light-emitting device
Technical Field
The present invention relates to a triphenylene derivative for an organic light-emitting element, a light-emitting device material containing the triphenylene derivative, and a light-emitting device, and more particularly, to a soluble organic compound having excellent color purity and high luminance and light-emitting efficiency, and an OLED device using the same.
Background
An Organic Light-Emitting Diode (OLED) for short. The light emitting device has a thin type and is capable of emitting light with high luminance at a low driving voltage and capable of emitting light with multiple colors by selecting a light emitting material, and thus is attracting attention.
Since the research revealed that the organic thin film element can emit light with high brightness by c.w. tang et al of kodak company, a large number of researchers in the OLED industry have made much research and progress for their applications. Organic thin film light emitting devices are widely used in various main display panels and the like, and the realization thereof has been greatly advanced.
Although research on organic electroluminescence is rapidly progressed, there are still many problems to be solved, such as improvement of External Quantum Efficiency (EQE), how to design and synthesize new materials with higher excellent purity, high efficiency of electron transport/hole blocking, and the like. For the organic electroluminescent device, the luminous quantum efficiency of the device is a comprehensive reflection of various factors and is also an important index for measuring the quality of the device.
Electroluminescence can be generally classified into fluorescence emission and phosphorescence emission. In fluorescence emission, an organic molecule in a singlet excited state transitions to a ground state, thereby emitting light. On the other hand, in phosphorescence, an organic molecule in a triplet excited state transitions to a ground state, thereby emitting light.
At present, some organic electroluminescent materials have been commercially used because of their excellent properties, but as host materials in organic electroluminescent devices, it is more important to have good hole transport properties in addition to triplet energy levels higher than guest materials, preventing energy back transfer by exciton transition release. Currently, materials that have both high triplet energy levels and good hole mobility in host materials are still lacking. Therefore, how to design new host materials with better performance is always a problem to be solved by those skilled in the art.
Disclosure of Invention
[ problem to be solved by the invention ]
As mentioned above, designing new better performing host materials is a problem that needs to be addressed at the present time.
The present invention is directed to a triphenylene derivative for an organic light-emitting element, a light-emitting device material containing the triphenylene derivative, and a light-emitting device, and more particularly, to a soluble organic compound having excellent color purity and high luminance and light-emitting efficiency, and an OLED device using the same.
The present invention provides a triphenylene derivative having the following general formula (1)
Wherein R1 is selected from the following substituted or unsubstituted substituents
Wherein R2, R3 are selected from the following substituted or unsubstituted substituents
Wherein R4, R5, R6, R7 are independently selected from hydrogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C4-C30 heteroaryl, or combinations thereof;
further preferred is that the organic compound is independently selected from the group consisting of
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The invention also provides application of the triphenylene-containing derivative in an organic light-emitting device.
Preferably, the organic light emitting device comprises an anode, a cathode and a plurality of organic functional layers positioned between the anode and the cathode, wherein the organic functional layers contain the triphenylene derivative.
The invention has the beneficial effects that:
the invention provides a triphenylene derivative, which has a structure shown in a general formula (1), has a medium triplet state energy level, and is designed into a bipolar material by adjusting substituent groups, so that the hole transmission capability and the electron transmission capability of the bipolar material are balanced, and the device performance is improved more favorably. In addition, the planar structure of the triphenylene is beneficial to stacking molecules, reducing unnecessary vibration energy loss and realizing high-efficiency luminous performance. The triphenylene derivative disclosed by the invention is simple in preparation method, easy to obtain raw materials and capable of meeting the industrial requirements.
The organic electroluminescent device of the present invention is a light emitting element comprising triphenylene derivatives, the light emitting element comprises a substrate, a first electrode, an organic layer, a second electrode and a cover layer, and the preferred device structure comprises the substrate, the first electrode positioned on the substrate, the organic layer positioned on the first electrode, the second electrode positioned on the organic layer and the cover layer positioned outside the second electrode.
The organic layer of the present invention may include a light emitting layer, a hole injecting layer, a hole transporting layer, an electron transporting layer, and an electron injecting layer as the structure of the organic layer. The organic layer of the light-emitting element may be formed of a single-layer structure, or may be formed of a multilayer structure including a light-emitting layer, a hole injection layer, a hole transport layer, an electron transport layer, and an electron injection layer; meanwhile, the organic layer may further include one or more layers, for example, the hole transport layer may include a first hole transport layer and a second hole transport layer. In the light-emitting element of the present invention, any material known in the art for the layer may be used for the other layers except that the light-emitting layer contains the triphenylene derivative of the present invention.
In the light-emitting element of the present invention, any substrate used in a typical organic light-emitting element can be used as the substrate material. Can be sodium glass or alkali-free glass or transparent flexible substrate, can be a substrate made of opaque materials such as silicon or stainless steel, and can be a flexible polyimide film. Different substrate materials have different properties and different application directions. The hole transporting layer of the present invention may be formed by a method of laminating or mixing one or two or more kinds of hole transporting materials, or a method of using a mixture of a hole transporting material and a polymer binder. Since a hole transport material is required to transport holes from the positive electrode with high efficiency between electrodes to which an electric field is applied, it is desirable that the hole transport material has high hole injection efficiency and can transport injected holes with high efficiency. Therefore, a hole transport material is required to have an appropriate ionization potential, an appropriate energy level, and a large hole mobility, and further to be excellent in material stability, and impurities which may become traps are not easily generated during manufacturing and use. The substance satisfying such conditions is not particularly limited, and may be, for example, carbazole derivatives, triarylamine derivatives, biphenyldiamine derivatives, fluorene derivatives, phthalocyanine compounds, hexanitrile hexaazabenzophenanthrene compounds, quinacridone compounds, perylene derivatives, anthraquinone compounds, F4-TCNQ, polyaniline, polythiophene, polyvinylcarbazole, and the like, but is not limited thereto.
As the light-emitting layer material of the present invention, in addition to the triphenylene derivative provided by the present invention, a doping material (also referred to as guest material) may be used and may contain a plurality of doping materials. In addition, the light-emitting layer can be a single light-emitting layer or can be a composite light-emitting layer which is transversely or longitudinally overlapped. The doping material may be selected from fluorescent material and phosphorescent material. The amount of the dopant is preferably 0.1 to 70% by mass, more preferably 0.1 to 30% by mass, still more preferably 1 to 20% by mass, and particularly preferably 1 to 10% by mass.
Fluorescent doping materials useful in the present invention may include: condensed polycyclic aromatic derivatives, styrylamine derivatives, condensed ring amine derivatives, boron-containing compounds, pyrrole derivatives, indole derivatives, carbazole derivatives, and the like, but are not limited thereto. Phosphorescent dopant materials useful in the present invention may include: heavy metal complexes, phosphorescent rare earth metal complexes, and the like, but are not limited thereto. Examples of the heavy metal complex include iridium complex, platinum complex, osmium complex and the like; examples of the rare earth metal complex include terbium complex and europium complex, but are not limited thereto. As the electron transport material of the present invention, a substance having good electron mobility is preferable, and both HOMO and LUMO energy levels are suitable. The electron transport materials that can be used in the present invention include: metal complexes, oxathiazole derivatives, oxazole derivatives, diazole derivatives, azabenzene derivatives, phenanthroline derivatives, diazoanthracene derivatives, silicon-containing heterocyclic compounds, boron-containing heterocyclic compounds, cyano compounds, quinoline derivatives, benzimidazole derivatives, and the like, but are not limited thereto.
As the electron transporting material of the present invention, a substance having an electron transporting ability and an effect of injecting electrons from a cathode are preferable, and excellent thin film forming ability is provided. The electron injecting material which can be used as the present invention includes: alkali metal compounds such as lithium oxide, lithium fluoride, lithium 8-hydroxyquinoline, lithium boron oxide, cesium carbonate, cesium 8-hydroxyquinoline, potassium silicate, calcium fluoride, calcium oxide, magnesium fluoride, magnesium oxide; fluorenone; nitrogen-containing five-membered ring derivatives, e.g. oxazole derivatives, oxadiazole derivatives, miaowAn azole derivative; a metal complex; anthraquinone dimethane, diphenoquinone, anthrone derivatives, and the like, but are not limited thereto, and these compounds may be used alone or in combination with other materials. As the cathode material of the present invention, a material having a low work function is preferable in order to easily inject electrons into the organic layer. Cathode materials useful in the present invention include: metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, aluminum, silver, tin, lead, or alloys thereof; and multilayer materials, e.g. LiF/Al or LiO 2 /Al, but is not limited thereto.
The organic layer materials of the present invention may be used alone to form a single layer structure, or may be mixed with other materials to form a single layer structure, or may be formed as a single layer laminated structure, a mixed single layer laminated structure, or a single layer laminated structure and a mixed single layer laminated structure. The organic electroluminescent device according to the present invention can be manufactured by sequentially laminating the above-described structures. The production method may be a known method such as a dry film forming method or a wet film forming method. Specific examples of the dry film forming method include vacuum deposition, sputtering, plasma, and ion plating. Specific examples of the wet film forming method include various coating methods such as spin coating, dipping, casting, and ink jet, but are not limited thereto. The organic light-emitting device can be widely applied to the fields of panel display, illumination light sources, flexible OLED, electronic paper, organic solar cells, organic photoreceptors or organic thin film transistors, indication boards, signal lamps and the like.
Detailed Description
The synthesis of the triphenylene derivative represented by the above general formula (1) can be carried out by a known method. For example, cross-coupling reactions using transition metals such as nickel, palladium, and the like. Other synthetic methods are C-C, C-N coupling reactions using transition metals such as magnesium or zinc. The reaction is limited to mild reaction conditions, excellent selectivity of various functional groups, and the like, and is preferably a Suzuki reaction or a Buchwald reaction.
The triphenylene derivatives of the invention are illustrated by the following examples, but are not limited to the triphenylene derivatives and the synthetic methods illustrated by these examples.
The initial raw materials and the solvent of the invention are purchased from Chinese medicines, and some common products such as OLED intermediates are purchased from domestic OLED intermediate manufacturers; various palladium catalysts, ligands, etc. are available from sigma-Aldrich.
1 H-NMR data were determined using a JEOL (400 MHz) nuclear magnetic resonance apparatus; HPLC data were determined using a Shimadzu LC-20AD high performance liquid meter.
The substances used in the examples and comparative examples are:
(Compound 1) 3, 6-bis (dibenzofuran-3-yl) -11, 13-diphenylphenanthrenequinazoline
(Compound 20) 3, 6-bis (9, 9-dimethyl-9H-fluoren-1-yl) -11, 13-diphenylphenanthrenequinazoline
(Compound 28) 3- (9, 9-dimethyl-9H-fluoren-4-yl) -6,11,13-triphenylphenanthrenequinazoline
(Compound 50) 6- (naphthalen-1-yl) -3- (naphthalen-8-yl) -11, 13-diphenylphenanthrenequinazoline
(Compound 67) 3, 6-bis (naphtholbenzofuran-10-yl) -11, 13-diphenylphenanthrenequinazoline
(Compound 109) 3, 6-bis (benzonaphthol thiophen-9-yl) -11, 13-diphenylphenanthrene quinazoline
(Compound 135) 11, 13-diphenyl-3, 6-bis (7-phenyl-7H-benzocarbazol-8-yl) phenanthrenequinazoline
(Compound 155) 10- (6- (naphthalen-2-yl) -11, 13-diphenylphenanthrenequinazolin-3-yl) -10H-benzoxazine
(Compound 179) 3- (dibenzofuran-2-yl) -6- (naphthalen-2-yl) -11, 13-diphenylphenanthrene quinazoline
(Compound 181) 3- (dibenzothiophen-4-yl) -6- (naphthalen-2-yl) -11, 13-diphenylphenanthrenequinazoline
(Compound 203) 11, 13-diphenyl-3, 6-bis (9-phenyl-9H-carbazol-2-yl) phenanthroquinazoline
(Compound 239) 3, 6-bis (naphthobenzofuran-4-yl) -11, 13-diphenylphenanthrenequinazoline
(Compound 270) 3, 6-bis (benzonaphthol thiophen-8-yl) -11, 13-diphenylphenanthrene quinazoline
(Compound 315) 3, 6-bis (9H-carbazol-9-yl) -11, 13-diphenylphenanthrenequinazoline
Example 1
Synthesis of Compound 1
50.5 g (100 mmol) of N- (7, 10-dibromoterphenyl-2-yl) benzamide and 12.5 g (120 mmol) of 2-chloropyridine in 300ml of dichloromethane were added to the flask under argon, cooled to-78℃and 31.0 g (110 mmol) of trifluoromethanesulfonic anhydride were then added, the reaction mixture was placed in an ice-water bath and heated to 0℃and 11 g (110 mmol) of benzonitrile were added. The reaction mixture was heated to 45 ℃ and reacted for 6 hours, cooled to room temperature, and triethylamine was added to neutralize the trifluoromethane sulfonate. The volatiles were removed under reduced pressure and flash column chromatography (eluent: 10% ethyl acetate in hexanes) afforded 51.9 g of 3, 6-dibromo-11, 13-diphenylphenanthrenequinazoline in 88% yield and 99.6% purity by HPLC.
1 HNMR(DMSO)：δ9.10(s，1H)，8.93(s，1H)，8.81(d,1H),8.35(m，2H),8.29(s，1H),8.12(s，1H),8.05～7.99(m，3H),7.80(d,2H),7.65(t，2H),7.50～7.49(m,4H)
59.0g (100 mmol) of 3, 6-dibromo-11, 13-diphenylphenanthrene quinazoline, 50.8g (240 mmol) of dibenzofuran-3-ylboronic acid, 1.16g (1.0 mmol) of tetrakis (triphenylphosphine) palladium, 200ml (300 mmol) of 1.5M aqueous sodium carbonate solution and 800ml (DME) of ethylene glycol dimethyl ether were added to the reactor under argon atmosphere, and the mixture was heated and stirred at 80℃for one night. Cooling to room temperature, adding 500ml of water, precipitating solid, filtering, washing the obtained solid with ethanol, obtaining 65.0g of compound 1, yield 85%, HPLC purity 99.3%.
1 HNMR (DMSO): delta 9.11 (d, 2H), 8.93 (s, 1H), 8.46 to 8.43 (m, 4H), 8.35 (d, 2H), 8.12 (s, 1H), 8.03 to 7.98 (m, 4H), 7.82 to 7.76 (m, 6H), 7.54 to 7.49 (m, 6H), 7.39 to 7.31 (m, 4H) example 2
Synthesis of Compound 20
50.5 g (100 mmol) of N- (7, 10-dibromoterphenyl-2-yl) benzamide and 12.5 g (120 mmol) of 2-chloropyridine in 300ml of dichloromethane were added to the flask under argon, cooled to-78℃and 31.0 g (110 mmol) of trifluoromethanesulfonic anhydride were then added, the reaction mixture was placed in an ice-water bath and heated to 0℃and 11 g (110 mmol) of benzonitrile were added. The reaction mixture was heated to 45 ℃ and reacted for 6 hours, cooled to room temperature, and triethylamine was added to neutralize the trifluoromethane sulfonate. The volatiles were removed under reduced pressure and flash column chromatography (eluent: 10% ethyl acetate in hexanes) afforded 51.9 g of 3, 6-dibromo-11, 13-diphenylphenanthrenequinazoline in 88% yield and 99.6% purity by HPLC.
1 HNMR(DMSO)：δ9.10(s，1H)，8.93(s，1H)，8.81(d,1H),8.35(m，2H),8.29(s，1H),8.12(s，1H),8.05～7.99(m，3H),7.80(d,2H),7.65(t，2H),7.50～7.49(m,4H)
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59.0g (100 mmol) of 3, 6-dibromo-11, 13-diphenylphenanthrenequinazoline, (9, 9-dimethyl-9H-fluoren-1-yl) boronic acid 57.1g (240 mmol), 1.16g (1.0 mmol) of tetrakis (triphenylphosphine) palladium, 200ml (300 mmol) of 1.5M aqueous sodium carbonate solution and 800ml (DME) of ethylene glycol dimethyl ether were charged into the reactor under argon atmosphere, and heated and stirred at 80℃overnight. Cooled to room temperature, 500ml of water was added, the solid was precipitated, filtered, and the obtained solid was washed with ethanol to obtain 71.9g of compound 20 in a yield of 88% and an HPLC purity of 99.5%.
1 HNMR(DMSO)：δ9.11(d，2H)，8.93(s，1H),8.46～8.43(m,4H),8.35(d，2H),8.12(s,1H),8.00(d,2H),7.90(d,2H),7.80(d,2H),7.68～7.65(m,4H),7.57～7.55(m,4H),7.50～7.49(m，4H),7.38(m,4H),7.28(m,4H),1.69(s,12H).
Example 3
Synthesis of Compound 28
Under argon, the reaction flask was charged with 46.0 g (100 mmol) of N- (7-bromo-10-chlorobenzo-2-yl) benzamide and 12.5 g (120 mmol) of 2-chloropyridine in 300ml of dichloromethane, cooled to-78℃and then 31.0 g (110 mmol) of trifluoromethanesulfonic anhydride was added, the reaction mixture was placed in an ice-water bath and heated to 0℃and 11 g (110 mmol) of benzonitrile was added. The reaction mixture was heated to 45 ℃ and reacted for 6 hours, cooled to room temperature, and triethylamine was added to neutralize the trifluoromethane sulfonate. Volatiles were removed under reduced pressure and flash column chromatography (eluent: 10% ethyl acetate in hexanes) afforded 46.3 g of 6-bromo-3-chloro-11, 13-diphenylphenanthrenequinazoline in 85% yield and 99.4% purity by HPLC.
1 HNMR(DMSO)：δ9.10(s，1H)，8.93(s，1H)，8.81(d,1H),8.35(m，2H),8.29(s，1H),8.12(s，1H),8.05～7.99(m，3H),7.80(d,2H),7.65(t，2H),7.50～7.49(m,4H)
54.6g (100 mmol) of 6-bromo-3-chloro-11, 13-diphenylphenanthrene quinazoline, 12.1g (100 mmol) of phenylboronic acid, 1.16g (1.0 mmol) of tetrakis (triphenylphosphine) palladium, 200ml (300 mmol) of 1.5M aqueous sodium carbonate solution and 800ml (DME) of ethylene glycol dimethyl ether were added to the reactor under argon atmosphere, and the mixture was heated and stirred at 80℃for one night. Cooling to room temperature, adding 500ml of water, precipitating solid, filtering, washing the obtained solid with ethanol to obtain 40.7g of 3-chloro-6,11,13-triphenylphenanthrene quinazoline, wherein the yield is 75%, and the HPLC purity is 99.1%.
1 HNMR(DMSO)：δ9.11(d，2H)，8.93(s，1H),8.86(d,1H),8.46～8.43(m,2H),8.35(d，2H),8.13～8.12(d,2H),7.89(d,1H),7.80～7.75(m,4H),7.50～7.49(m，6H),7.41(m,1H).
54.3g (100 mmol) of 3-chloro-6,11,13-triphenylphenanthrenequinazoline, (9, 9-dimethyl-9H-fluoren-4-yl) boronic acid 28.6g (120 mmol), 1.16g (1.0 mmol) of tetrakis (triphenylphosphine) palladium, 200ml (300 mmol) of 1.5M aqueous sodium carbonate solution and 800ml (DME) of ethylene glycol dimethyl ether were added to the reactor under argon atmosphere, and the mixture was heated and stirred at 80℃overnight. Cooled to room temperature, 500ml of water was added, the solid precipitated, filtered, and the resulting solid was washed with ethanol to give 55.3g of compound 28 in 79% yield and 99.7% purity by HPLC.
1 HNMR(DMSO)：δ9.11(d，2H)，8.93(s，1H),8.46～8.43(m,4H),8.35(d，2H),8.12(s,1H),7.90(d,1H),7.80～7.75(m,5H),7.65(m,3H),7.55～7.49(m,7H),7.47～7.41(m,2H),1.69(s,6H).
Example 4
Synthesis of Compound 50
Under argon, the reaction flask was charged with 46.0 g (100 mmol) of N- (7-bromo-10-chlorobenzo-2-yl) benzamide and 12.5 g (120 mmol) of 2-chloropyridine in 300ml of dichloromethane, cooled to-78℃and then 31.0 g (110 mmol) of trifluoromethanesulfonic anhydride was added, the reaction mixture was placed in an ice-water bath and heated to 0℃and 11 g (110 mmol) of benzonitrile was added. The reaction mixture was heated to 45 ℃ and reacted for 6 hours, cooled to room temperature, and triethylamine was added to neutralize the trifluoromethane sulfonate. Volatiles were removed under reduced pressure and flash column chromatography (eluent: 10% ethyl acetate in hexanes) afforded 46.3 g of 6-bromo-3-chloro-11, 13-diphenylphenanthrenequinazoline in 85% yield and 99.4% purity by HPLC.
1 HNMR(DMSO)：δ9.10(s，1H)，8.93(s，1H)，8.81(d,1H),8.35(m，2H),8.29(s，1H),8.12(s，1H),8.05～7.99(m，3H),7.80(d,2H),7.65(t，2H),7.50～7.49(m,4H)
54.6g (100 mmol) of 6-bromo-3-chloro-11, 13-diphenylphenanthrene quinazoline, 172.0g (100 mmol) of 1-naphthalene boronic acid, 1.16g (1.0 mmol) of tetrakis (triphenylphosphine) palladium, 200ml (300 mmol) of 1.5M aqueous sodium carbonate solution and 800ml (DME) of ethylene glycol dimethyl ether were added to the reactor under argon atmosphere, and the mixture was heated and stirred at 80℃overnight. Cooling to room temperature, adding 500ml of water, precipitating solid, filtering, washing the obtained solid with ethanol, obtaining 42.7g of 3-chloro-6- (naphthalene-1-yl) -11, 13-diphenyl phenanthrene quinazoline, the yield is 72%, and the HPLC purity is 99.1%.
1 HNMR(DMSO)：δ9.11(d，2H)，8.95～8.93(m，2H),8.86(d,1H),8.50(d，1H)，8.46～8.43(m,2H),8.35(d，2H),8.20(d,1H),8.13～8.12(d,2H),8.09(d,1H),7.89(d,1H),7.80～7.77(m,3H),7.65(m,2H),7.52～7.49(m,5H),7.39(d,1H).
59.3g (100 mmol) of 3-chloro-6- (naphthalen-1-yl) -11, 13-diphenylphenanthrene quinazoline, 31.4g (120 mmol) of naphtho [1,2-b ] benzofuran-8-ylboronic acid, 1.16g (1.0 mmol) of tetrakis (triphenylphosphine) palladium, 200ml (300 mmol) of 1.5M aqueous sodium carbonate solution and 800ml (DME) were introduced into the reactor under argon atmosphere, and heated and stirred at 80℃overnight. Cooled to room temperature, 500ml of water was added, the solid was precipitated, filtered, and the obtained solid was washed with ethanol to obtain 62.8g of compound 50 in a yield of 81% and an HPLC purity of 99.5%.
1 HNMR(DMSO)：δ9.11(d，2H)，8.95～8.93(m，2H),8.50(d，1H)，8.46～8.43(m,4H),8.35(d，2H),8.20～8.16(m,2H),8.12～8.11(d,2H),8.09(d,1H),7.88～7.83(m,3H),7.80～7.77(m,4H),7.69～7.65(m,4H),7.52～7.48(m,6H),7.39(m,1H).
Example 5
Synthesis of Compound 67
50.5 g (100 mmol) of N- (7, 10-dibromoterphenyl-2-yl) benzamide and 12.5 g (120 mmol) of 2-chloropyridine in 300ml of dichloromethane were added to the flask under argon, cooled to-78℃and 31.0 g (110 mmol) of trifluoromethanesulfonic anhydride were then added, the reaction mixture was placed in an ice-water bath and heated to 0℃and 11 g (110 mmol) of benzonitrile were added. The reaction mixture was heated to 45 ℃ and reacted for 6 hours, cooled to room temperature, and triethylamine was added to neutralize the trifluoromethane sulfonate. The volatiles were removed under reduced pressure and flash column chromatography (eluent: 10% ethyl acetate in hexanes) afforded 51.9 g of 3, 6-dibromo-11, 13-diphenylphenanthrenequinazoline in 88% yield and 99.6% purity by HPLC.
1 HNMR(DMSO)：δ9.10(s，1H)，8.93(s，1H)，8.81(d,1H),8.35(m，2H),8.29(s，1H),8.12(s，1H),8.05～7.99(m，3H),7.80(d,2H),7.65(t，2H),7.50～7.49(m,4H)
59.0g (100 mmol) of 3, 6-dibromo-11, 13-diphenylphenanthrene quinazoline, 62.9g (240 mmol) of naphthobenzofuran-10-ylboronic acid, 1.16g (1.0 mmol) of tetrakis (triphenylphosphine) palladium, 200ml (300 mmol) of 1.5M aqueous sodium carbonate solution and 800ml (DME) of ethylene glycol dimethyl ether were charged into the reactor under argon atmosphere, and heated and stirred at 80℃overnight. Cooled to room temperature, 500ml of water was added, the solid precipitated, filtered, and the resulting solid was washed with ethanol to give 72.7g of compound 67 in a yield of 84% and an HPLC purity of 99.3%.
1 HNMR(DMSO)：δ9.11(d，2H)，8.93(s，1H),8.46～8.43(m,4H),8.35(d，2H),8.16(d,2H),8.12～8.11(m,3H),8.08(d,2H),8.02(m,2H),7.84～7.80(m,4H),7.69～7.67(m,4H),7.65(d,2H),7.51～7.48(m,8H).
Example 6
Synthesis of Compound 109
50.5 g (100 mmol) of N- (7, 10-dibromoterphenyl-2-yl) benzamide and 12.5 g (120 mmol) of 2-chloropyridine in 300ml of dichloromethane were added to the flask under argon, cooled to-78℃and 31.0 g (110 mmol) of trifluoromethanesulfonic anhydride were then added, the reaction mixture was placed in an ice-water bath and heated to 0℃and 11 g (110 mmol) of benzonitrile were added. The reaction mixture was heated to 45 ℃ and reacted for 6 hours, cooled to room temperature, and triethylamine was added to neutralize the trifluoromethane sulfonate. The volatiles were removed under reduced pressure and flash column chromatography (eluent: 10% ethyl acetate in hexanes) afforded 51.9 g of 3, 6-dibromo-11, 13-diphenylphenanthrenequinazoline in 88% yield and 99.6% purity by HPLC.
1 HNMR(DMSO)：δ9.10(s，1H)，8.93(s，1H)，8.81(d,1H),8.35(m，2H),8.29(s，1H),8.12(s，1H),8.05～7.99(m，3H),7.80(d,2H),7.65(t，2H),7.50～7.49(m,4H)
59.0g (100 mmol) of 3, 6-dibromo-11, 13-diphenylphenanthrene quinazoline, 66.8g (240 mmol) of benzonaphthol thiophen-9-ylboronic acid, 1.16g (1.0 mmol) of tetrakis (triphenylphosphine) palladium, 200ml (300 mmol) of 1.5M aqueous sodium carbonate solution and 800ml (DME) of ethylene glycol dimethyl ether were charged into the reactor under argon atmosphere, and heated and stirred at 80℃for one night. Cooled to room temperature, 500ml of water was added, the solid was precipitated, filtered, and the obtained solid was washed with ethanol to obtain 74.5g of compound 109, yield 83%, and HPLC purity 99.4%.
1 HNMR(DMSO)：δ9.11(d，2H)，8.93(s，1H),8.54(m,2H),8.46～8.43(m，4H),8.35(d,2H),8.24～8.17(m,6H),7.99(d,2H),7.80～7.78(m,6H),7.65～7.61(m,4H),7.53～7.50(m,5H).
Example 7
Synthesis of Compound 135
50.5 g (100 mmol) of N- (7, 10-dibromoterphenyl-2-yl) benzamide and 12.5 g (120 mmol) of 2-chloropyridine in 300ml of dichloromethane were added to the flask under argon, cooled to-78℃and 31.0 g (110 mmol) of trifluoromethanesulfonic anhydride were then added, the reaction mixture was placed in an ice-water bath and heated to 0℃and 11 g (110 mmol) of benzonitrile were added. The reaction mixture was heated to 45 ℃ and reacted for 6 hours, cooled to room temperature, and triethylamine was added to neutralize the trifluoromethane sulfonate. The volatiles were removed under reduced pressure and flash column chromatography (eluent: 10% ethyl acetate in hexanes) afforded 51.9 g of 3, 6-dibromo-11, 13-diphenylphenanthrenequinazoline in 88% yield and 99.6% purity by HPLC.
1 HNMR(DMSO)：δ9.10(s，1H)，8.93(s，1H)，8.81(d,1H),8.35(m，2H),8.29(s，1H),8.12(s，1H),8.05～7.99(m，3H),7.80(d,2H),7.65(t，2H),7.50～7.49(m,4H)
59.0g (100 mmol) of 3, 6-dibromo-11, 13-diphenylphenanthrenequinazoline, (7-phenyl-7H-benzocarbazol-8-yl) boric acid (80.9 g (240 mmol), 1.16g (1.0 mmol) of tetrakis (triphenylphosphine) palladium, 200ml (300 mmol) of 1.5M aqueous sodium carbonate solution and 800ml (DME) of ethylene glycol dimethyl ether were charged into the reactor under argon atmosphere, and heated and stirred at 80℃overnight. Cooled to room temperature, 500ml of water was added, the solid was precipitated, filtered, and the obtained solid was washed with ethanol to obtain 87.4g of compound 135, yield 86%, and HPLC purity 99.5%.
1 HNMR(DMSO)：δ9.11(d，2H)，8.93(s，1H),8.54(m,2H),8.46～8.43(m，4H),8.35(d,2H),8.29(d,2H),8.12(s,1H),8.06～7.94(m,8H),7.80(d,2H),7.65～7.61(m,7H),7.58(d,2H),7.53(d,2H),7.50(m,7H),7.48(m,2H).
Example 8
Synthesis of Compound 155
Under argon, the reaction flask was charged with 46.0 g (100 mmol) of N- (7-bromo-10-chlorobenzo-2-yl) benzamide and 12.5 g (120 mmol) of 2-chloropyridine in 300ml of dichloromethane, cooled to-78℃and then 31.0 g (110 mmol) of trifluoromethanesulfonic anhydride was added, the reaction mixture was placed in an ice-water bath and heated to 0℃and 11 g (110 mmol) of benzonitrile was added. The reaction mixture was heated to 45 ℃ and reacted for 6 hours, cooled to room temperature, and triethylamine was added to neutralize the trifluoromethane sulfonate. Volatiles were removed under reduced pressure and flash column chromatography (eluent: 10% ethyl acetate in hexanes) afforded 46.3 g of 6-bromo-3-chloro-11, 13-diphenylphenanthrenequinazoline in 85% yield and 99.4% purity by HPLC.
1 HNMR(DMSO)：δ9.10(s，1H)，8.93(s，1H)，8.81(d,1H),8.35(m，2H),8.29(s，1H),8.12(s，1H),8.05～7.99(m，3H),7.80(d,2H),7.65(t，2H),7.50～7.49(m,4H)
54.6g (100 mmol) of 6-bromo-3-chloro-11, 13-diphenylphenanthrene quinazoline, 172.0g (100 mmol) of 2-naphthaleneboronic acid, 1.16g (1.0 mmol) of tetrakis (triphenylphosphine) palladium, 200ml (300 mmol) of 1.5M aqueous sodium carbonate solution and 800ml (DME) of ethylene glycol dimethyl ether were added to the reactor under argon atmosphere, and the mixture was heated and stirred at 80℃overnight. Cooling to room temperature, adding 500ml of water, precipitating solid, filtering, washing the obtained solid with ethanol, obtaining 42.7g of 3-chloro-6- (naphthalene-1-yl) -11, 13-diphenyl phenanthrene quinazoline, the yield is 72%, and the HPLC purity is 99.1%.
1 HNMR(DMSO)：δ9.11(d，2H)，8.93(d，1H),8.86(d,1H),8.46～8.43(m,2H),8.35(d,2H),8.13～8.12(m,2H),8.09～7.99(m,3H),7.89(m,1H),7.80(m,2H),7.65～7.63(m,3H),7.60(m,1H),7.55(d,1H),7.50～7.49(m,4H),7.38(d,1H).
To the reaction vessel was added 26.9 g (240 mmol) of potassium tert-butoxide, 648 mg (1 mmol%) of 3-chloro-6- (naphthalen-1-yl) -11, 13-diphenylphenanthrenequinazoline (59.3 g (100 mmol), 22.0 g (120 mmol) of 10H benzoxazine and 1000mL of ethylene glycol dimethyl ether (DME) as catalyst, [1, 3-bis (2, 6-di-isopropylphenyl) -4, 5-dihydroimidazol-2-ylidene ] chloro ] [ 3-phenylallyl ] palladium (II), and the mixture was heated and stirred at 80℃for 15 hours under argon atmosphere. The reaction mixture was cooled to room temperature, 500ml of water was added, and the mixture was filtered, and the crude product was purified by silica gel column chromatography (eluent: ethyl acetate/hexane) to give 59.9 g of compound 155, purity of HPLC was 99.3%, yield was 81%.
1 HNMR(DMSO)：δ9.11(d，2H)，8.93(d，1H),8.88(d,1H),8.46～8.43(m,2H),8.35(d,2H),8.12(s,1H),8.09～8.06(m,2H),7.99(d,1H),7.90(s,1H),7.80(d,2H),7.66～7.63(m,4H),7.60(m,1H),7.50～7.49(m,4H),7.38(d,1H),7.14(d,2H),7.01～6.96(m,6H).
Example 9
Synthesis of Compound 179
Under argon, the reaction flask was charged with 46.0 g (100 mmol) of N- (7-bromo-10-chlorobenzo-2-yl) benzamide and 12.5 g (120 mmol) of 2-chloropyridine in 300ml of dichloromethane, cooled to-78℃and then 31.0 g (110 mmol) of trifluoromethanesulfonic anhydride was added, the reaction mixture was placed in an ice-water bath and heated to 0℃and 11 g (110 mmol) of benzonitrile was added. The reaction mixture was heated to 45 ℃ and reacted for 6 hours, cooled to room temperature, and triethylamine was added to neutralize the trifluoromethane sulfonate. Volatiles were removed under reduced pressure and flash column chromatography (eluent: 10% ethyl acetate in hexanes) afforded 46.3 g of 6-bromo-3-chloro-11, 13-diphenylphenanthrenequinazoline in 85% yield and 99.4% purity by HPLC.
1 HNMR(DMSO)：δ9.10(s，1H)，8.93(s，1H)，8.81(d,1H),8.35(m，2H),8.29(s，1H),8.12(s，1H),8.05～7.99(m，3H),7.80(d,2H),7.65(t，2H),7.50～7.49(m,4H)
54.6g (100 mmol) of 6-bromo-3-chloro-11, 13-diphenylphenanthrene quinazoline, 172.0g (100 mmol) of 2-naphthaleneboronic acid, 1.16g (1.0 mmol) of tetrakis (triphenylphosphine) palladium, 200ml (300 mmol) of 1.5M aqueous sodium carbonate solution and 800ml (DME) of ethylene glycol dimethyl ether were added to the reactor under argon atmosphere, and the mixture was heated and stirred at 80℃overnight. Cooling to room temperature, adding 500ml of water, precipitating solid, filtering, washing the obtained solid with ethanol, obtaining 42.7g of 3-chloro-6- (naphthalene-1-yl) -11, 13-diphenyl phenanthrene quinazoline, the yield is 72%, and the HPLC purity is 99.1%.
1 HNMR(DMSO)：δ9.11(d，2H)，8.93(d，1H),8.86(d,1H),8.46～8.43(m,2H),8.35(d,2H),8.13～8.12(m,2H),8.09～7.99(m,3H),7.89(m,1H),7.80(m,2H),7.65～7.63(m,3H),7.60(m,1H),7.55(d,1H),7.50～7.49(m,4H),7.38(d,1H).
59.3g (100 mmol) of 3-chloro-6- (naphthalen-1-yl) -11, 13-diphenylphenanthrenequinazoline, 25.4g (120 mmol) of dibenzofuran-2-ylboronic acid, [1, 3-bis (2, 6-di-isopropylphenyl) -4, 5-dihydroimidazol-2-ylidene, were introduced into a reaction vessel under argon atmosphere]Chlorine][ 3-phenylallyl group]The palladium (II) catalyst 648 mg, 200ml (300 mmol) of 1.5M aqueous sodium carbonate and 1000ml (DME) of ethylene glycol dimethyl ether were stirred at 80℃overnight. Cooling to room temperature, adding 800ml of water, separating out solid, filtering, washing the obtained solid with ethanol, recrystallizing with 500ml of toluene to obtain 58.0g of compound 179, yield 80% and HPLC purity 99.5%. 1 HNMR(DMSO)：δ9.11(d，2H)，8.93(d，1H),8.46～8.43(m,2H),8.35(d,2H),
8.12(s,1H),8.09～7.99(m,3H),7.98(d,1H),7.88～7.83(m,2H),7.80～7.79(m,3H),7.65～7.63(m,3H),7.60(m,1H),7.50～7.49(m,4H),7.39～7.38(m,2H),7.31(m,1H).
Example 10
Synthesis of Compound 181
Under argon, the reaction flask was charged with 46.0 g (100 mmol) of N- (7-bromo-10-chlorobenzo-2-yl) benzamide and 12.5 g (120 mmol) of 2-chloropyridine in 300ml of dichloromethane, cooled to-78℃and then 31.0 g (110 mmol) of trifluoromethanesulfonic anhydride was added, the reaction mixture was placed in an ice-water bath and heated to 0℃and 11 g (110 mmol) of benzonitrile was added. The reaction mixture was heated to 45 ℃ and reacted for 6 hours, cooled to room temperature, and triethylamine was added to neutralize the trifluoromethane sulfonate. Volatiles were removed under reduced pressure and flash column chromatography (eluent: 10% ethyl acetate in hexanes) afforded 46.3 g of 6-bromo-3-chloro-11, 13-diphenylphenanthrenequinazoline in 85% yield and 99.4% purity by HPLC.
1 HNMR(DMSO)：δ9.10(s，1H)，8.93(s，1H)，8.81(d,1H),8.35(m，2H),8.29(s，1H),8.12(s，1H),8.05～7.99(m，3H),7.80(d,2H),7.65(t，2H),7.50～7.49(m,4H)
54.6g (100 mmol) of 6-bromo-3-chloro-11, 13-diphenylphenanthrene quinazoline, 172.0g (100 mmol) of 2-naphthaleneboronic acid, 1.16g (1.0 mmol) of tetrakis (triphenylphosphine) palladium, 200ml (300 mmol) of 1.5M aqueous sodium carbonate solution and 800ml (DME) of ethylene glycol dimethyl ether were added to the reactor under argon atmosphere, and the mixture was heated and stirred at 80℃overnight. Cooling to room temperature, adding 500ml of water, precipitating solid, filtering, washing the obtained solid with ethanol, obtaining 42.7g of 3-chloro-6- (naphthalene-1-yl) -11, 13-diphenyl phenanthrene quinazoline, the yield is 72%, and the HPLC purity is 99.1%.
1 HNMR(DMSO)：δ9.11(d，2H)，8.93(d，1H),8.86(d,1H),8.46～8.43(m,2H),8.35(d,2H),8.13～8.12(m,2H),8.09～7.99(m,3H),7.89(m,1H),7.80(m,2H),7.65～7.63(m,3H),7.60(m,1H),7.55(d,1H),7.50～7.49(m,4H),7.38(d,1H).
59.3g (100 mmol) of 3-chloro-6- (naphthalen-1-yl) -11, 13-diphenylphenanthrenequinazoline, 27.3g (120 mmol) of dibenzothiophen-4-ylboronic acid, [1, 3-bis (2, 6-di-isopropylphenyl) -4, 5-dihydroimidazol-2-ylidene ] chloro ] [ 3-phenylallyl ] palladium (II) catalyst 648 mg, 200ml (300 mmol) of 1.5M aqueous sodium carbonate solution and 1000ml (DME) of ethylene glycol dimethyl ether were charged in a reaction vessel under argon atmosphere, and heated and stirred at 80℃overnight. Cooling to room temperature, adding 800ml of water, separating out solid, filtering, washing the obtained solid with ethanol, recrystallizing with 500ml of toluene to obtain 63.0g of compound 181, yield 85% and HPLC purity 99.3%.
1 HNMR(DMSO)：δ9.11(d，2H)，8.93(d，1H),8.55(m,1H),8.46～8.43(m,5H),8.35～8.32(m,3H),8.12(s,1H),8.09～7.99(m,3H),7.93(d,1H),7.80(m,2H),7.70(m,1H),7.65～7.63(m,3H),7.60(m,1H),7.56～7.55(m,2H),7.50～7.49(m,5H),7.38(d,1H).
Example 11
Synthesis of Compound 203
50.5 g (100 mmol) of N- (7, 10-dibromoterphenyl-2-yl) benzamide and 12.5 g (120 mmol) of 2-chloropyridine in 300ml of dichloromethane were added to the flask under argon, cooled to-78℃and 31.0 g (110 mmol) of trifluoromethanesulfonic anhydride were then added, the reaction mixture was placed in an ice-water bath and heated to 0℃and 11 g (110 mmol) of benzonitrile were added. The reaction mixture was heated to 45 ℃ and reacted for 6 hours, cooled to room temperature, and triethylamine was added to neutralize the trifluoromethane sulfonate. The volatiles were removed under reduced pressure and flash column chromatography (eluent: 10% ethyl acetate in hexanes) afforded 51.9 g of 3, 6-dibromo-11, 13-diphenylphenanthrenequinazoline in 88% yield and 99.6% purity by HPLC.
1 HNMR(DMSO)：δ9.10(s，1H)，8.93(s，1H)，8.81(d,1H),8.35(m，2H),8.29(s，1H),8.12(s，1H),8.05～7.99(m，3H),7.80(d,2H),7.65(t，2H),7.50～7.49(m,4H)
59.0g (100 mmol) of 3, 6-dibromo-11, 13-diphenylphenanthrenequinazoline, (9-phenyl-9H-carbazol-2-yl) boric acid 68.9g (240 mmol), 1.16g (1.0 mmol) of tetrakis (triphenylphosphine) palladium, 200ml (300 mmol) of 1.5M aqueous sodium carbonate solution and 800ml (DME) of ethylene glycol dimethyl ether were charged into the reactor under argon atmosphere, and heated and stirred at 80℃overnight. Cooled to room temperature, 500ml of water was added, the solid was precipitated, filtered, and the obtained solid was washed with ethanol to obtain 73.2g of compound 203 in a yield of 80% and an HPLC purity of 99.3%.
1 HNMR(DMSO)：δ9.11(d，2H)，8.93(s，1H),8.55(d,2H),8.46～8.43(m，4H),8.35(d,2H),8.31(d,2H),8.12(s,1H),7.94～7.91(m,4H),7.80(d,2H),7.74(s,2H),7.65～7.62(m,6H),7.58(m,2H),7.50～7.49(m,8H),7.35(d,2H),7.16(d,2H).
Example 12
Synthesis of Compound 239
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50.5 g (100 mmol) of N- (7, 10-dibromoterphenyl-2-yl) benzamide and 12.5 g (120 mmol) of 2-chloropyridine in 300ml of dichloromethane were added to the flask under argon, cooled to-78℃and 31.0 g (110 mmol) of trifluoromethanesulfonic anhydride were then added, the reaction mixture was placed in an ice-water bath and heated to 0℃and 11 g (110 mmol) of benzonitrile were added. The reaction mixture was heated to 45 ℃ and reacted for 6 hours, cooled to room temperature, and triethylamine was added to neutralize the trifluoromethane sulfonate. The volatiles were removed under reduced pressure and flash column chromatography (eluent: 10% ethyl acetate in hexanes) afforded 51.9 g of 3, 6-dibromo-11, 13-diphenylphenanthrenequinazoline in 88% yield and 99.6% purity by HPLC.
1 HNMR(DMSO)：δ9.10(s，1H)，8.93(s，1H)，8.81(d,1H),8.35(m，2H),8.29(s，1H),8.12(s，1H),8.05～7.99(m，3H),7.80(d,2H),7.65(t，2H),7.50～7.49(m,4H)
59.0g (100 mmol) of 3, 6-dibromo-11, 13-diphenylphenanthrene quinazoline, 62.9g (240 mmol) of naphthobenzofuran-4-ylboronic acid, 1.16g (1.0 mmol) of tetrakis (triphenylphosphine) palladium, 200ml (300 mmol) of 1.5M aqueous sodium carbonate solution and 800ml (DME) of ethylene glycol dimethyl ether were charged into the reactor under argon atmosphere, and heated and stirred at 80℃overnight. Cooled to room temperature, 500ml of water was added, the solid was precipitated, filtered, and the obtained solid was washed with ethanol to obtain 70.9g of compound 239, yield 82%, and HPLC purity 99.5%.
1 HNMR(DMSO)：δ9.11(d，2H)，8.93(s，1H),8.46～8.43(m,4H),8.35(d，2H),8.28(d,2H),8.12(s,1H),8.11～8.02(m,6H),7.80(d,2H),7.75(d，2H),7.51～7.50(m,5H),7.49(s,2H),7.42(s,2H).
Example 13
Synthesis of Compound 270
50.5 g (100 mmol) of N- (7, 10-dibromoterphenyl-2-yl) benzamide and 12.5 g (120 mmol) of 2-chloropyridine in 300ml of dichloromethane were added to the flask under argon, cooled to-78℃and 31.0 g (110 mmol) of trifluoromethanesulfonic anhydride were then added, the reaction mixture was placed in an ice-water bath and heated to 0℃and 11 g (110 mmol) of benzonitrile were added. The reaction mixture was heated to 45 ℃ and reacted for 6 hours, cooled to room temperature, and triethylamine was added to neutralize the trifluoromethane sulfonate. The volatiles were removed under reduced pressure and flash column chromatography (eluent: 10% ethyl acetate in hexanes) afforded 51.9 g of 3, 6-dibromo-11, 13-diphenylphenanthrenequinazoline in 88% yield and 99.6% purity by HPLC.
1 HNMR(DMSO)：δ9.10(s，1H)，8.93(s，1H)，8.81(d,1H),8.35(m，2H),8.29(s，1H),8.12(s，1H),8.05～7.99(m，3H),7.80(d,2H),7.65(t，2H),7.50～7.49(m,4H)
59.0g (100 mmol) of 3, 6-dibromo-11, 13-diphenylphenanthrene quinazoline, 66.8g (240 mmol) of naphthobenzofuran-4-ylboronic acid, 1.16g (1.0 mmol) of tetrakis (triphenylphosphine) palladium, 200ml (300 mmol) of 1.5M aqueous sodium carbonate solution and 800ml (DME) of ethylene glycol dimethyl ether were charged into the reactor under argon atmosphere, and heated and stirred at 80℃overnight. Cooled to room temperature, 500ml of water was added, the solid was precipitated, filtered, and the obtained solid was washed with ethanol to obtain 74.5g of compound 270 in a yield of 83% and an HPLC purity of 99.5%.
1 HNMR(DMSO)：δ9.11(d，2H)，8.93(s，1H),8.55～8.54(m,4H),8.46～8.43(m,4H),8.35(d，2H),8.32(d,2H),8.12(s,1H),7.99(m,2H),7.80(m,4H),7.78(d,2H),7.70(d,2H),7.65～7.61(m,4H),7.53(m,2H),7.50(m,3H).
Example 14
Synthesis of Compound 315
50.5 g (100 mmol) of N- (7, 10-dibromoterphenyl-2-yl) benzamide and 12.5 g (120 mmol) of 2-chloropyridine in 300ml of dichloromethane were added to the flask under argon, cooled to-78℃and 31.0 g (110 mmol) of trifluoromethanesulfonic anhydride were then added, the reaction mixture was placed in an ice-water bath and heated to 0℃and 11 g (110 mmol) of benzonitrile were added. The reaction mixture was heated to 45 ℃ and reacted for 6 hours, cooled to room temperature, and triethylamine was added to neutralize the trifluoromethane sulfonate. The volatiles were removed under reduced pressure and flash column chromatography (eluent: 10% ethyl acetate in hexanes) afforded 51.9 g of 3, 6-dibromo-11, 13-diphenylphenanthrene [9,10-g ] quinazoline in 88% yield and 99.6% HPLC purity.
1 HNMR(DMSO)：δ9.10(s，1H)，8.93(s，1H)，8.81(d,1H),8.35(m，2H),8.29(s，1H),8.12(s，1H),8.05～7.99(m，3H),7.80(d,2H),7.65(t，2H),7.50～7.49(m,4H)
26.9 g (240 mmol) of potassium tert-butoxide, [1, 3-bis (2, 6-di-isopropylphenyl) -4, 5-dihydroimidazol-2-ylidene ] chloro ] [ 3-phenylallyl ] palladium (II) catalyst 648 mg (1 mmol%) of 3, 6-dibromo-11, 13-diphenylphenanthrene [9,10-g ] quinazoline 59.0g (100 mmol), carbazole 40.1 g (200 mmol) and 1000mL of ethylene glycol dimethyl ether (DME) were charged in a reaction vessel under argon atmosphere, and heated and stirred at 80℃for 15 hours. The reaction mixture was cooled to room temperature, 500ml of water was added, filtration was carried out, and the crude product was purified by silica gel column chromatography (eluent: ethyl acetate/hexane) to give 61.0 g of 3, 6-bis (9H-carbazol-9-yl) -11, 13-diphenylphenanthrene [9,10-g ] quinazoline, purity by HPLC was 99.5%, yield 80%.
1 HNMR(DMSO)：δ9.05(d，2H)，8.93(s,1H),8.55(d,2H),8.35(d,2H),8.25～8.24(m，2H),8.19(m,2H),8.11(m，3H),8.00(m,1H),7.94(d,2H),7.80(m,2H)7.65(m,2H),7.58(m,2H),7.50～7.49(m,6H),7.35(d,2H),7.20(d,2H),7.16(d,2H).
Device embodiments
Evaluation of light emitting material device
The organic layer compounds used in the device examples are shown below:
example 15
The preparation method of the device comprises the following steps:
the basic structure model of the device is as follows: ITO/HAT-CN (10 nm)/TAPC (40 nm)/TCTA (10 nm)/EML: RD (Ir complex) (40 nm) =94: 6/ETL (30 nm)/LiF (1 nm)/Al (80 nm)
Transparent anodic Indium Tin Oxide (ITO) 20 (10Ω/sq) glass substrate was ultrasonically cleaned using acetone, ethanol, and distilled water in this order, and then treated with ozone plasma for 15 minutes.
Then, an ITO substrate was mounted on a substrate holder of a vacuum vapor deposition apparatus. In the vapor deposition equipment, the pressure of the system is controlled to be 10 -6 And (5) a bracket. The hole transport layer material HAT-CN was evaporated onto the ITO substrate to a thickness of 60 nm.
The luminescent layer material EML (compound 1) with a thickness of 40nm was then evaporated, wherein different mass fractions of the RD metal iridium complex dopant were doped.
The electron transport layer material ETL having a thickness of 30nm is then evaporated.
LiF having a thickness of 1nm was then evaporated as an electron injection layer.
Finally, al with the thickness of 80nm is evaporated to serve as a cathode, and the device is packaged by using a glass packaging cover.
Example 16
The same components as in example 20 were evaluated except that the EML material was compound 20, and the test results are shown in table 1.
Example 17
The same components as in example 20 were evaluated except that the EML material was compound 28, and the test results are shown in table 1.
Example 18
The same components as in example 20 were evaluated except that the EML material was compound 50, and the test results are shown in table 1.
Example 19
The same components as in example 20 were evaluated except that the EML material was compound 67, and the test results are shown in table 1.
Example 20
The same components as in example 20 were evaluated except that the EML material was compound 109, and the test results are shown in table 1.
Example 21
The same components as in example 20 were evaluated except that the EML material was compound 135, and the test results are shown in table 1.
Example 22
The same components as in example 20 were evaluated except that the EML material was compound 155, and the test results are shown in table 1.
Example 23
The same components as in example 20 were evaluated except that the EML material was compound 179, and the test results are shown in table 1.
Example 24
The same components as in example 20 were evaluated except that the EML material was compound 181, and the test results are shown in table 1.
Example 25
The same components as in example 20 were evaluated except that the EML material was compound 203, and the test results are shown in table 1.
Example 26
The same components as in example 20 were evaluated except that the EML material was compound 239, and the test results are shown in table 1.
Example 27
The same components as in example 20 were evaluated except that the EML material was compound 270, and the test results are shown in table 1.
Example 28
The same components as in example 20 were evaluated except that the EML material was compound 315, and the test results are shown in table 1.
Comparative example 1
The same components as in example 20 were evaluated except that the EML material was compound RH-01, and the test results are shown in Table 1.
Comparative example 2
The same components as in example 20 were evaluated except that the EML material was compound RH-02, and the test results are shown in Table 1.
[ Table 1 ]
Sequence number Main body material Current (mA/cm) 2 ) Current efficiency (cd/A) LT98(hr)
Example 15 1 10 16.8 11.0
Example 16 20 10 16.1 11.8
Example 17 28 10 16.7 12.1
Example 18 50 10 15.9 13.3
Example 19 67 10 14.8 12.3
Example 20 109 10 16.5 14.2
Example 21 135 10 15.9 11.9
Example 22 155 10 14.7 12.3
Example 23 179 10 16.9 11.8
Example 24 181 10 17.1 12.8
Example 25 203 10 16.3 11.7
Example 26 239 10 15.4 11.6
Example 27 270 10 15.9 12.3
Example 28 315 10 15.3 12.6
Comparative example 1 RH01 10 9.7 10.8
Comparative example 2 RH02 10 8.2 10.7
Except for different luminescent layers, the device structures are consistent, the performances of devices based on RH-01 and RH-02 are used as references, the current efficiency of triphenylene derivatives is obviously improved, and the service life of the devices is prolonged. In conclusion, the novel triphenylene derivative organic material prepared by the invention has a great application value on an organic light-emitting diode.

Claims (7)

1. A triphenylene derivative, wherein the triphenylene derivative is selected from the group consisting of:
2. an organic optoelectronic device, comprising:
a first electrode;
a second electrode facing the first electrode;
an organic functional layer sandwiched between the first electrode and the second electrode;
wherein the organic functional layer comprises the triphenylene derivative of claim 1.
3. The organic optoelectronic device according to claim 2, wherein the organic optoelectronic device is an organic photovoltaic device, an organic light emitting device, an electronic paper, an organic photoreceptor, an organic thin film transistor, or an organic memory device.
4. An organic photoelectric element comprising a cathode layer, an anode layer and an organic layer, wherein the organic layer comprises at least one layer of a hole injection layer, a hole transport layer, a light emitting layer or an active layer, an electron injection layer and an electron transport layer, and the organic photoelectric element is characterized in that: any layer of the device contains the triphenylene derivative of claim 1.
5. The organic photoelectric element according to claim 4, wherein the light-emitting layer contains the organic compound according to claim 1 and a corresponding guest material, wherein the mass percentage of the organic compound is 1% to 99%, and the guest material is not limited.
6. The organic photoelectric element according to claim 4, wherein the electron transport layer contains the organic compound, and wherein the mass percentage of the organic compound is 1% to 100%.
7. A display or lighting device, characterized in that it comprises an organic optoelectronic element according to any one of claims 4-6.
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